TW202007643A - Method for manufacturing a graphitic sheet - Google Patents

Method for manufacturing a graphitic sheet Download PDF

Info

Publication number
TW202007643A
TW202007643A TW107126560A TW107126560A TW202007643A TW 202007643 A TW202007643 A TW 202007643A TW 107126560 A TW107126560 A TW 107126560A TW 107126560 A TW107126560 A TW 107126560A TW 202007643 A TW202007643 A TW 202007643A
Authority
TW
Taiwan
Prior art keywords
substrate
composite substrate
octadecyltrichlorosilane
graphite sheet
semi
Prior art date
Application number
TW107126560A
Other languages
Chinese (zh)
Other versions
TWI675799B (en
Inventor
謝淑貞
Original Assignee
國立中山大學
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 國立中山大學 filed Critical 國立中山大學
Priority to TW107126560A priority Critical patent/TWI675799B/en
Priority to US16/120,494 priority patent/US10787366B2/en
Application granted granted Critical
Publication of TWI675799B publication Critical patent/TWI675799B/en
Publication of TW202007643A publication Critical patent/TW202007643A/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00—Manufacture or treatment of microstructural devices or systems
    • B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
    • B81C2201/0147—Film patterning
    • B81C2201/0149—Forming nanoscale microstructures using auto-arranging or self-assembling material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/165—Monolayers, e.g. Langmuir-Blodgett
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A method for manufacturing a graphitic sheet is used to obtain the graphitic sheet with similar characteristics to graphene. The method includes forming an ocatadecyltrichlorosilanelayer on a substrate to obtain a composite. The composite is annealed at 250-400℃ for 30-90 minutes, forming the graphitic sheet on the substrate via self-assembly of ocatadecyltrichlorosilane in the ocatadecyltrichlorosilane layer. The annealed composite is immersed in water, followed by being sonicated for 2 minutes with a frequency of 40 kHz and a power output of 200 W, to separate the graphitic sheet from the substrate.

Description

石墨片製造方法 Graphite sheet manufacturing method

本發明係關於一種石墨片製造方法，尤其是一種與石墨烯具有類似特性的石墨片之石墨片製造方法。 The invention relates to a method for manufacturing graphite flakes, in particular to a method for manufacturing graphite flakes having similar characteristics to graphene.

石墨烯(graphene)係呈蜂巢狀晶格(honeycomb crystal lattice)之平面薄膜，為僅具有一個碳原子厚度(約為0.34nm)之二維材料，其具有高機械強度、熱傳導及高載子轉移率等優異特性，能夠應用於多種領域。 Graphene is a planar thin film with a honeycomb crystal lattice. It is a two-dimensional material with only one carbon atom thickness (approximately 0.34 nm). It has high mechanical strength, thermal conductivity, and high carrier transfer. Excellent characteristics such as rate, can be applied to various fields.

然而，石墨烯多以習知化學氣相層積法(chemical vapor deposition，CVD)製備而成，製備過程繁瑣。有鑑於此，若是能夠以簡單的製程即能夠製造獲得與石墨烯具有類似特性的石墨片，將對石墨烯的相關應用產業上帶來極大的助益。 However, graphene is mostly prepared by the conventional chemical vapor deposition (CVD) method, and the preparation process is cumbersome. In view of this, if a simple process can be used to produce graphite sheets with similar characteristics to graphene, it will bring great benefits to the related application industry of graphene.

為解決上述問題，本發明的目的是提供一種石墨片製造方法係用以製造獲得與石墨烯具有類似特性的石墨片者。 In order to solve the above problems, an object of the present invention is to provide a method for manufacturing graphite flakes for producing graphite flakes having similar characteristics to graphene.

本發明的石墨片製造方法，包含：於一基板上形成一十八烷基三氯矽烷層，得一複合基板；於250~400℃之溫度下，對該複合基板進行退火30~90分鐘，使該十八烷基三氯矽烷層中的十八烷基三氯矽烷自行組裝形成附著於該基板上的石墨片；及將經退火之複合基板浸入水中，在40KHz 之頻率、200瓦之功率下，進行超音波震盪2分鐘，使該石墨片脫離該基板。 The method for manufacturing graphite sheet of the present invention includes: forming an octadecyltrichlorosilane layer on a substrate to obtain a composite substrate; annealing the composite substrate at a temperature of 250-400°C for 30-90 minutes, The octadecyltrichlorosilane in the octadecyltrichlorosilane layer is self-assembled to form a graphite sheet attached to the substrate; and the annealed composite substrate is immersed in water at a frequency of 40KHz and a power of 200 watts Next, ultrasonically oscillate for 2 minutes to detach the graphite sheet from the substrate.

依據上述，藉由前述的石墨片製造方法，即能夠製造獲得與石墨烯具有類似特性的石墨片(晶格間距約為0.24nm、厚度約為0.34nm)，因此可以作為石墨烯的替代物，例如能夠作為表面增強拉曼散射活性基板使用，應用於分析一待測樣品中的雙酚A的濃度，為本發明之功效。 According to the above, by the aforementioned graphite sheet manufacturing method, it is possible to manufacture graphite sheets with similar characteristics to graphene (lattice spacing about 0.24 nm, thickness about 0.34 nm), so it can be used as a substitute for graphene, For example, it can be used as a surface-enhanced Raman scattering active substrate, which is used to analyze the concentration of bisphenol A in a sample to be tested, which is the effect of the present invention.

本發明的石墨片製造方法另包含：於該基板上形成該十八烷基三氯矽烷層包含：將該基板置入一十八烷基三氯矽烷溶液中，於25~35℃之溫度下靜置24小時，得一複合基板半成品；及於115℃之溫度下，對將該複合基板半成品進行退火10分鐘；如此有助於在該基板上形成厚度均一的十八烷基三氯矽烷層。 The manufacturing method of the graphite sheet of the present invention further comprises: forming the octadecyltrichlorosilane layer on the substrate comprises: placing the substrate in an octadecyltrichlorosilane solution at a temperature of 25~35°C After standing for 24 hours, a composite substrate semi-finished product is obtained; and the composite substrate semi-finished product is annealed at 115°C for 10 minutes; this helps to form a layer of octadecyltrichlorosilane with a uniform thickness on the substrate .

本發明的石墨片製造方法另包含：將十八烷基三氯矽烷溶於一溶劑中，以得該十八烷基三氯矽烷溶液，該溶劑為十六烷、甲苯、氯仿或二氯甲烷；如此能夠藉由該溶劑的選擇，使十八烷基三氯矽烷能夠均勻分布於該十八烷基三氯矽烷溶液中。 The method for manufacturing graphite sheet of the present invention further comprises: dissolving octadecyltrichlorosilane in a solvent to obtain the octadecyltrichlorosilane solution, and the solvent is hexadecane, toluene, chloroform or dichloromethane ; By this choice of solvent, octadecyltrichlorosilane can be evenly distributed in the octadecyltrichlorosilane solution.

本發明的石墨片製造方法另包含：對該複合基板半成品進行退火前，以至少一潤洗液潤洗該複合基板半成品，以去除該複合基板半成品上的雜質及殘留物；較佳地，以該至少一潤洗液潤洗該複合基板半成品包含：依序以一第一潤洗液、一第二潤洗液及一第三潤洗液潤洗該複合基板半成品，該第一潤洗液、該第二潤洗液及該第三潤洗液分別為氯仿、異丙醇及去離子水；如此藉由該第一潤洗液、該第二潤洗液及該第三潤洗液的使用，可以去除該複合基板半成品上的雜質及殘留物，以避免該雜質及該殘留物對後續製程造成的影響。 The graphite sheet manufacturing method of the present invention further includes: before annealing the semi-finished product of the composite substrate, rinse the semi-finished product of the composite substrate with at least one washing solution to remove impurities and residues on the semi-finished product of the composite substrate; preferably, Rinsing the semi-finished product of the composite substrate with the at least one rinse solution includes: sequentially rinse the semi-finished product of the composite substrate with a first rinse solution, a second rinse solution, and a third rinse solution, the first rinse solution , The second lotion and the third lotion are chloroform, isopropanol and deionized water; so by the first lotion, the second lotion and the third lotion After use, the impurities and residues on the semi-finished product of the composite substrate can be removed to avoid the influence of the impurities and the residues on the subsequent process.

本發明的石墨片製造方法中，該基板為一矽晶片；如此，藉由該矽晶片的平整表面，使該烷基三氯矽烷層中的烷基三氯矽烷層能夠形成矽 氧鍵結(Si-O bond)，因而該矽晶片可以作為支撐所形成的石墨片之良好基板。 In the graphite sheet manufacturing method of the present invention, the substrate is a silicon wafer; thus, the flat surface of the silicon wafer enables the alkyl trichlorosilane layer in the alkyl trichlorosilane layer to form a silicon-oxygen bond ( Si-O bond), so the silicon wafer can be used as a good substrate to support the formed graphite sheet.

〔第1圖〕試驗(B)中各組待測樣品的拉曼光譜曲線。 [Figure 1] Raman spectrum curve of each group of test samples in test (B).

〔第2圖〕試驗(C)中各組待測樣品的拉曼光譜曲線。 [Figure 2] Raman spectrum curve of each group of test samples in test (C).

〔第3圖〕試驗(D)中各組待測樣品的拉曼光譜曲線。 [Figure 3] Raman spectrum curve of each group of test samples in test (D).

〔第4圖〕試驗(E)中各組待測樣品的拉曼光譜曲線。 [Figure 4] Raman spectrum curve of each group of test samples in test (E).

為讓本發明之上述及其他目的、特徵及優點能更明顯易懂，下文特舉本發明之較佳實施例，並配合所附圖式，作詳細說明如下：本發明之石墨片製造方法的一實施例中，係藉由形成於一基板上的十八烷基三氯矽烷(ocatadecyltrichlorosilane，簡稱OTS)層的自組裝作用，得以於該基板上成形一石墨片，該石墨片之晶格間距約為0.24nm，且厚度約為0.34nm，與石墨烯具有類似特性。 In order to make the above and other objects, features and advantages of the present invention more obvious and understandable, the preferred embodiments of the present invention are described below in conjunction with the attached drawings, which are described in detail as follows: In one embodiment, by self-assembly of an octadecyltrichlorosilane (OTS) layer formed on a substrate, a graphite sheet can be formed on the substrate, and the lattice spacing of the graphite sheet It is about 0.24nm and the thickness is about 0.34nm, which has similar characteristics to graphene.

詳而言之，工者係可以藉由塗佈、噴灑等任何習知方式於該基板上形成該十八烷基三氯矽烷層。於本實施例中，係可以將作為該基板的一矽晶片置入一十八烷基三氯矽烷溶液(濃度為1M)中，並於25~35℃之溫度下靜置24小時，得一複合基板半成品，接著再於115℃之溫度下，對該複合基板半成品進行退火(annealing)10分鐘，得一複合基板，該複合基板包含該基板及形成於該基板上的該十八烷基三氯矽烷層。又，該十八烷基三氯矽烷溶液包含十八烷基三氯矽烷及一溶劑，該溶劑可以為十六烷 (hexadecane)、甲苯(tolune)、氯仿(chloroform)或二氯甲烷(dichloromethane)，使十八烷基三氯矽烷能夠均勻分布於該十八烷基三氯矽烷溶液中。 In detail, the worker can form the octadecyltrichlorosilane layer on the substrate by any conventional method such as coating and spraying. In this embodiment, a silicon wafer as the substrate can be placed in an octadecyltrichlorosilane solution (concentration: 1M) and allowed to stand at a temperature of 25 to 35°C for 24 hours. The composite substrate semi-finished product is then annealed at 115°C for 10 minutes to obtain a composite substrate including the substrate and the octadecyl trioxide formed on the substrate Chlorosilane layer. In addition, the octadecyltrichlorosilane solution contains octadecyltrichlorosilane and a solvent, and the solvent may be hexadecane, tolune, chloroform or dichloromethane So that octadecyltrichlorosilane can be evenly distributed in the octadecyltrichlorosilane solution.

此外，為了去除附著於該複合基板半成品上的雜質及殘留物，進而防止該雜質及殘留物影響後續的製程效率，可以在對該複合基板半成品進行退火前，以至少一潤洗液潤洗該複合基板半成品。於本實施例中，係依許使用一第一潤洗液、一第二潤洗液及一第三潤洗液潤洗該複合基板半成品，該第一潤洗液、該第二潤洗液及該第三潤洗液分別為氯仿、異丙醇(isopropanol)及去離子水(deionized water)。 In addition, in order to remove impurities and residues adhering to the semi-finished product of the composite substrate and thereby prevent the impurities and residues from affecting subsequent process efficiency, the semi-finished product of the composite substrate may be rinsed with at least one rinse solution before annealing Composite substrate semi-finished products. In this embodiment, a first rinse solution, a second rinse solution and a third rinse solution are used to rinse the semi-finished composite substrate, the first rinse solution and the second rinse solution And the third lotion is chloroform, isopropanol and deionized water.

接著於高溫下對該複合基板進行退火，使該十八烷基三氯矽烷層中的十八烷基三氯矽烷能夠進行該自組裝作用。於本實施例中，係於250~400℃之溫度下，對該複合基板進行退火30~90分鐘，此時該十八烷基三氯矽烷層中的十八烷基三氯矽烷即能夠進行該自組裝作用，進而形成附著於該基板上的石墨片。 Next, the composite substrate is annealed at a high temperature, so that the octadecyltrichlorosilane in the octadecyltrichlorosilane layer can perform the self-assembly function. In this embodiment, the composite substrate is annealed at a temperature of 250-400°C for 30-90 minutes. At this time, the octadecyltrichlorosilane in the octadecyltrichlorosilane layer can be performed. The self-assembly action further forms a graphite sheet attached to the substrate.

進一步，工者即可以自該基板上分離該石墨片。於本實施例中，係將經退火之複合基板浸泡於水中，在40KHz之頻率、200瓦之功率下，進行超音波震盪2分鐘，即可以使該石墨片脫離該基板，取得該石墨片。 Further, the worker can separate the graphite sheet from the substrate. In this embodiment, the annealed composite substrate is immersed in water and subjected to ultrasonic vibration at a frequency of 40 KHz and a power of 200 watts for 2 minutes, so that the graphite sheet can be detached from the substrate to obtain the graphite sheet.

為證實經該石墨片製造方法所製造獲得的石墨片確實與石墨烯具有類似特性，且可以作為表面增強拉曼散射活性基板(surface-enhanced Raman spectroscopy active substrate)使用，應用於分析待測樣品中的雙酚A的濃度，遂進行以下試驗： In order to confirm that the graphite sheet manufactured by the graphite sheet manufacturing method does have similar characteristics with graphene, and can be used as a surface-enhanced Raman spectroscopy active substrate (surface-enhanced Raman spectroscopy active substrate), used in the analysis of the sample to be tested The concentration of bisphenol A was then tested as follows:

(A)石墨片的特性分析 (A) Characteristic analysis of graphite sheet

依據穿透式電子顯微鏡(transmission electron microscopy，簡稱TEM)及高解析場發射穿透式電子顯微鏡(high-resolution transmission electron microscopy，簡稱HRTEM)的分析結果可以得知，經該石墨片製造方法所製造獲得的石墨片具有0.24nm的晶格間距(lattice spacing)，與石墨烯的晶格常數(lattice constant)相同。另依據原子力顯微鏡(atomic force microscopy，簡稱AFM)的表面形貌分析(surface topography)結果顯示，該石墨片的厚度約為0.34nm，與石墨烯的層間距(interlayer spacing)相當。依據上述，該石墨片確實具有與石墨烯類似的特性。 According to the analysis results of transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM), it can be known that the graphite sheet manufacturing method The obtained graphite sheet has a lattice spacing of 0.24 nm, which is the same as the lattice constant of graphene. According to the surface topography analysis results of atomic force microscopy (AFM), the thickness of the graphite sheet is about 0.34 nm, which is equivalent to the interlayer spacing of graphene. Based on the above, the graphite sheet does have similar characteristics to graphene.

(B)石墨片作為表面增強拉曼散射活性基板的使用 (B) Use of graphite sheets as active substrate for surface enhanced Raman scattering

本試驗係以雙酚A(bisphenol A，簡稱BPA)作為待測樣品，將雙酚A溶解於乙醇(即，95%的乙醇水溶液)中，以形成0.1M的雙酚A溶液，將2μL的雙酚A溶液滴在該石墨片(第B1組)或該矽晶片(第B2組)上，使該雙酚A溶液於室溫下乾燥後，進行拉曼光譜的分析，使用波長為532nm的雷射光，其功率為21.9mM。本試驗另以該石墨片(第B3組)及該矽晶片(第B4組)作為比較。 In this test, bisphenol A (BPA) was used as the sample to be tested, and bisphenol A was dissolved in ethanol (ie, 95% ethanol aqueous solution) to form a 0.1M bisphenol A solution. The bisphenol A solution was dropped on the graphite sheet (Group B1) or the silicon wafer (Group B2). After the bisphenol A solution was dried at room temperature, Raman spectroscopy analysis was performed using a wavelength of 532 nm Laser light has a power of 21.9mM. In this experiment, the graphite sheet (Group B3) and the silicon wafer (Group B4) were used for comparison.

請參照第1圖所示，第B3組的拉曼光譜曲線僅於1341cm-1及1602cm-1處具有波峰，而第B1及B2組的拉曼光譜曲線則於1121cm-1、1188cm-1、1240cm-1、1269cm-1、1621cm-1及3072cm-1處具有波峰，然而比較第B1及B2組的拉曼光譜曲線可以得知，儘管以第B1組的石墨片或以第B2組的矽晶片均可以測得雙酚A的訊號，惟以B1組的石墨片所測得的強度明顯優於以第B2組的矽晶片所測得者，顯示該石墨片確實能夠作為表面增強拉曼散射活性基板使用。 Please refer to Figure 1. The Raman spectrum curves of group B3 only have peaks at 1341cm -1 and 1602cm -1 , while the Raman spectrum curves of groups B1 and B2 are at 1121cm -1 , 1188cm -1 , There are peaks at 1240cm -1 , 1269cm -1 , 1621cm -1 and 3072cm -1 . However, comparing the Raman spectrum curves of groups B1 and B2, it can be seen that although the graphite flakes of group B1 or the silicon of group B2 The bisphenol A signal can be measured on the wafer, but the intensity measured with the graphite sheet of group B1 is significantly better than that measured with the silicon wafer of group B2, showing that the graphite sheet can indeed be used as surface-enhanced Raman scattering Active substrate use.

(C)對雙酚A的靈敏度 (C) Sensitivity to bisphenol A

本試驗係分別將濃度為10-1M(第C1組)、10-2M(第C2組)、10-3M(第C3組)、10-4M(第C4組)、10-5M(第C5組)及10-6M(第C6組)的雙酚A溶液作為待測樣品，續進行拉曼光譜的分析。 In this test, the concentrations were 10 -1 M (Group C1), 10 -2 M (Group C2), 10 -3 M (Group C3), 10 -4 M (Group C4), 10 -5 The bisphenol A solutions of M (Group C5) and 10 -6 M (Group C6) were used as samples to be tested, and the analysis of Raman spectroscopy was continued.

請參照第2圖所示，縱使針對濃度僅為10-6M的雙酚A溶液(第C6組)，藉由該石墨片的使用仍能夠有效測得雙酚A的訊號，且該濃度已遠低於歐盟對雙酚A的遷移限制(specific migration limit，簡稱SML)，即遷移至每公斤食物中的雙酚A不得高於0.6mg(經換算約為2.6μM)。 Please refer to the figure 2, even for the bisphenol A solution with a concentration of only 10 -6 M (Group C6), the signal of bisphenol A can still be effectively measured by the use of the graphite sheet, and the concentration has been It is far below the EU's specific migration limit (SML) for bisphenol A, that is, the bisphenol A migrated into each kilogram of food should not exceed 0.6mg (about 2.6μM after conversion).

(D)各種塑膠用品的雙酚A之遷移量 (D) Migration of bisphenol A from various plastic products

本試驗係將兩種不同的塑膠湯匙(第D1、D2組)、嬰兒奶瓶(第D3組)、可重複使用的夾鏈袋(第D4組)及密封食品容器(第D5組)作為待測樣品，將各組待測樣品與80℃之熱水接觸1小時，再進行拉曼光譜的分析。本試驗另以濃度為10-4M的雙酚A溶液(第D6組)作為比較。 In this test, two different plastic spoons (Group D1, D2), baby bottle (Group D3), reusable chain bag (Group D4) and sealed food container (Group D5) were tested. For samples, each group of samples to be tested was contacted with hot water at 80°C for 1 hour, and then analyzed by Raman spectroscopy. In this test, a bisphenol A solution (Group D6) with a concentration of 10 -4 M was used as a comparison.

請參照第3圖所示，依據鄰近1121cm-1處的波峰(即，第3圖星號處)之波峰面積進行換算的結果，可以得知各組的待測樣品的雙酚A之遷移量約分別為1×10-5、3.2×10-6、2×10-5、1×10-6及6.3×10-7M。 Please refer to Figure 3, based on the conversion of the peak area near the peak at 1121cm -1 (that is, the asterisk in Figure 3), you can know that the migration amount of bisphenol A in each group of test samples is about They are 1×10 -5 , 3.2×10 -6 , 2×10 -5 , 1×10 -6 and 6.3×10 -7 M, respectively.

(E)鹽類濃度對偵測效果的影響 (E) The effect of salt concentration on the detection effect

本試驗係以濃度為10-3M的雙酚A溶液作為待測樣品，並於其中加入氯化鈉溶液，使各組待測樣品的氯化鈉濃度分別為0M(第E1組)、0.025M(第E2組)、0.05M(第E3組)、0.1M(第E4組)、0.25M(第E5組)、0.5M(第E6組)、1M(第E7組)及2M(第E8組)，續進行拉曼光譜的分析。 In this test, the bisphenol A solution with a concentration of 10 -3 M was used as the test sample, and sodium chloride solution was added to it, so that the sodium chloride concentration of each group of test samples was 0M (group E1), 0.025 M (Group E2), 0.05M (Group E3), 0.1M (Group E4), 0.25M (Group E5), 0.5M (Group E6), 1M (Group E7) and 2M (Group E8) Group), continue Raman spectroscopy analysis.

請參照第4圖所示，隨著氯化鈉濃度的升高，雙酚A的訊號強度有逐漸降低的現象，然而在與人類血清樣品與人類尿液樣品相似的氯化鈉離子強度(人類血清樣品與人類尿液樣品的氯化鈉離子強度分別為0.14M及0.17M)下，仍可以清楚地測得雙酚A的訊號強度，顯示該石墨片不僅能夠適用於檢測含鹽溶液中的雙酚A，亦適用於檢測體液(如，血清或尿液)中的雙酚A。 As shown in Figure 4, as the sodium chloride concentration increases, the signal strength of bisphenol A gradually decreases. However, the sodium chloride ion strength (human) is similar to that of human serum samples and human urine samples. Under the sodium ion ionic strength of serum samples and human urine samples of 0.14M and 0.17M, respectively, the signal strength of bisphenol A can still be clearly measured, showing that the graphite sheet is not only suitable for the detection of saline solution Bisphenol A is also suitable for detecting bisphenol A in body fluids (eg, serum or urine).

綜上所述，藉由前述的石墨片製造方法，即能夠製造獲得與石墨烯具有類似特性的石墨片(晶格間距約為0.24nm、厚度約為0.34nm)，因此可以作為石墨烯的替代物，例如能夠作為表面增強拉曼散射活性基板使用，應用於分析待測樣品中的雙酚A的濃度，為本發明之功效。 In summary, the aforementioned graphite sheet manufacturing method can produce graphite sheets with similar characteristics to graphene (lattice spacing is about 0.24nm, thickness is about 0.34nm), so it can be used as a substitute for graphene The substance, for example, can be used as a surface-enhanced Raman scattering active substrate, and is used to analyze the concentration of bisphenol A in a sample to be tested, which is the effect of the present invention.

雖然本發明已利用上述較佳實施例揭示，然其並非用以限定本發明，任何熟習此技藝者在不脫離本發明之精神和範圍之內，相對上述實施例進行各種更動與修改仍屬本發明所保護之技術範疇，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed using the above-mentioned preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with this art without departing from the spirit and scope of the present invention still makes various changes and modifications to the above-mentioned embodiments. The technical scope of the invention is protected, so the scope of protection of the present invention shall be subject to the scope defined in the appended patent application.

Claims (6)

一種石墨片製造方法，包含：於一基板上形成一十八烷基三氯矽烷層，得一複合基板；於250~400℃之溫度下，對該複合基板進行退火30~90分鐘，使該十八烷基三氯矽烷層中的十八烷基三氯矽烷自行組裝形成附著於該基板上的石墨片；及將經退火之複合基板浸入水中，在40KHz之頻率、200瓦之功率下，進行超音波震盪2分鐘，使該石墨片脫離該基板。 A method for manufacturing graphite sheets, comprising: forming an octadecyltrichlorosilane layer on a substrate to obtain a composite substrate; annealing the composite substrate at a temperature of 250-400°C for 30-90 minutes to make the The octadecyltrichlorosilane in the octadecyltrichlorosilane layer is self-assembled to form a graphite sheet attached to the substrate; and the annealed composite substrate is immersed in water at a frequency of 40KHz and a power of 200 watts. Ultrasonic vibration was performed for 2 minutes to detach the graphite sheet from the substrate. 如申請專利範圍第1項所述之石墨片製造方法，其中，於該基板上形成該十八烷基三氯矽烷層包含：將該基板置入一十八烷基三氯矽烷溶液中，於25~35℃之溫度下靜置24小時，得一複合基板半成品；及於115℃之溫度下，對將該複合基板半成品進行退火10分鐘。 The method for manufacturing a graphite sheet as described in item 1 of the patent application scope, wherein forming the octadecyltrichlorosilane layer on the substrate comprises: placing the substrate in an octadecyltrichlorosilane solution, in Let stand for 24 hours at a temperature of 25 to 35°C to obtain a semi-finished composite substrate; and at a temperature of 115°C, anneal the semi-finished composite substrate for 10 minutes. 如申請專利範圍第2項所述之石墨片製造方法，另包含：將十八烷基三氯矽烷溶於一溶劑中，以得該十八烷基三氯矽烷溶液，該溶劑為十六烷、甲苯、氯仿或二氯甲烷。 The method for manufacturing graphite flakes as described in item 2 of the patent application scope further includes: dissolving octadecyltrichlorosilane in a solvent to obtain the octadecyltrichlorosilane solution, the solvent being hexadecane , Toluene, chloroform or methylene chloride. 如申請專利範圍第2項所述之石墨片製造方法，另包含：對該複合基板半成品進行退火前，以至少一潤洗液潤洗該複合基板半成品，以去除該複合基板半成品上的雜質及殘留物。 The method for manufacturing graphite sheet as described in item 2 of the patent application scope further includes: before annealing the semi-finished product of the composite substrate, rinse the semi-finished product of the composite substrate with at least one washing solution to remove impurities and the semi-finished product of the composite substrate the remains. 如申請專利範圍第4項所述之石墨片製造方法，其中，以該至少一潤洗液潤洗該複合基板半成品包含：依序以一第一潤洗液、一第二潤洗液及一第三潤洗液潤洗該複合基板半成品，該第一潤洗液、該第二潤洗液及該第三潤洗液分別為氯仿、異丙醇及去離子水。 The method for manufacturing graphite sheet as described in item 4 of the patent application scope, wherein the semi-finished product of the composite substrate with the at least one washing liquid comprises: a first washing liquid, a second washing liquid and a A third rinse liquid rinses the semi-finished composite substrate. The first rinse liquid, the second rinse liquid, and the third rinse liquid are chloroform, isopropyl alcohol, and deionized water, respectively. 如申請專利範圍第1~5項中任一項所述之石墨片製造方法， 其中，該基板為一矽晶片。 The method for manufacturing a graphite sheet according to any one of items 1 to 5 of the patent application range, wherein the substrate is a silicon wafer.
TW107126560A 2018-07-31 2018-07-31 Method for manufacturing a graphitic sheet TWI675799B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
TW107126560A TWI675799B (en) 2018-07-31 2018-07-31 Method for manufacturing a graphitic sheet
US16/120,494 US10787366B2 (en) 2018-07-31 2018-09-04 Method for manufacturing graphitic sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW107126560A TWI675799B (en) 2018-07-31 2018-07-31 Method for manufacturing a graphitic sheet

Publications (2)

Publication Number Publication Date
TWI675799B TWI675799B (en) 2019-11-01
TW202007643A true TW202007643A (en) 2020-02-16

Family

ID=69188633

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107126560A TWI675799B (en) 2018-07-31 2018-07-31 Method for manufacturing a graphitic sheet

Country Status (2)

Country Link
US (1) US10787366B2 (en)
TW (1) TWI675799B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073048B (en) * 2012-12-24 2015-04-22 陕西科技大学 Method for preparing patterned ZnO film by liquid phase self-assembly technology
US10272647B2 (en) * 2014-12-19 2019-04-30 Corning Incorporated Graphene and polymer-free method for transferring CVD grown graphene onto hydrophobic substrates
US9941380B2 (en) * 2015-11-30 2018-04-10 Taiwan Semiconductor Manufacturing Co., Ltd. Graphene transistor and related methods
US10369775B2 (en) * 2016-12-09 2019-08-06 Imec Vzw Method of releasing graphene from substrate

Also Published As

Publication number Publication date
US20200039829A1 (en) 2020-02-06
TWI675799B (en) 2019-11-01
US10787366B2 (en) 2020-09-29

Similar Documents

Publication Publication Date Title
Schranghamer et al. Review and comparison of layer transfer methods for two-dimensional materials for emerging applications
Metzger et al. Biaxial strain in graphene adhered to shallow depressions
Huang et al. Anisotropic thermal conductivity in 2D tellurium
Zuo et al. Transparent, flexible surface enhanced Raman scattering substrates based on Ag-coated structured PET (polyethylene terephthalate) for in-situ detection
Zhang et al. Improved thermal stability of graphene-veiled noble metal nanoarrays as recyclable SERS substrates
WO2015149116A1 (en) Graphene process and product
Kim et al. Ultrasensitive and stable plasmonic surface-enhanced Raman scattering substrates covered with atomically thin monolayers: Effect of the insulating property
Braeuninger-Weimer et al. Fast, noncontact, wafer-scale, atomic layer resolved imaging of two-dimensional materials by ellipsometric contrast micrography
CN103969241A (en) Raman base
Li et al. Scalable transfer of suspended two-dimensional single crystals
Wang et al. High-fidelity transfer of chemical vapor deposition grown 2D transition metal dichalcogenides via substrate decoupling and polymer/small molecule composite
Huo et al. Few-layer antimonene: Large yield synthesis, exact atomical structure and outstanding optical limiting
Prasad et al. Ripple mediated surface enhanced Raman spectroscopy on graphene
Michalak et al. Investigation of the chemical purity of silicon surfaces reacted with liquid methanol
Qu et al. Evaporable glass-state molecule-assisted transfer of clean and intact graphene onto arbitrary substrates
Xu et al. Electrical and optical properties of 4-N, N-dimethylamino-4′-N′-methyl-stilbazolium tosylate (DAST) modified by carbon nanotubes
Kato et al. Fabrication and optical characterization of Si nanowires formed by catalytic chemical etching in Ag2O/HF solution
Hu et al. Large‐Scale Suspended Graphene Used as a Transparent Substrate for Infrared Spectroscopy
Uda et al. Electrical DNA biosensor using aluminium interdigitated electrode for Salmonella detection
Humbert et al. Linear and nonlinear optical properties of functionalized CdSe quantum dots prepared by plasma sputtering and wet chemistry
Singh et al. DNA hybridization on silicon nanowires
CN102507671A (en) Porous silicon biochip and preparation method thereof
TWI675799B (en) Method for manufacturing a graphitic sheet
Li et al. Protection of molecular microcrystals by encapsulation under single-layer graphene
CN107037027B (en) A kind of preparation method of wide area surface enhancing Raman scattering substrate